JP2010180366A - Fluororesin composition and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluororesin composition that has excellent moldability with relatively high MFR (Melt Flow Rate) as well as excellent adhesion to an elastomer and does not produce foam even when processed at elevated temperatures. <P>SOLUTION: The fluororesin composition includes a fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group, and an amino group at the end of the main chain or the end of the side chain of the polymer, and an aromatic-based unsymmetrical polyfunctional compound, the aromatic-based unsymmetrical polyfunctional compound being 0.05-10.0 pts.mass based on the 100 pts.mass of the fluororesin. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a fluororesin composition and a laminate.

Conventionally, due to the recent increase in environmental awareness, the development of laws to prevent fuel volatilization has progressed. Especially in the automobile industry, there is a significant tendency to suppress fuel volatilization, especially in the United States, and there is a great need for materials with excellent fuel barrier properties. It is becoming. Thermoplastic resins such as polyphenylene sulfide resins, ethylene vinyl alcohol resins, and liquid crystal polyester resins are used as materials with excellent fuel barrier properties, but these materials have high fuel barrier properties but are flexible. It is scarce and difficult to use for parts that require flexibility. In contrast, rubber-based materials have high flexibility but generally have poor fuel barrier properties. When used in automotive parts such as fuel hoses, volatilization and transpiration of fuel are large, and improvements are required. It has been. In order to solve these problems, in recent years, a fuel hose having a laminated structure including a resin layer having a high fuel barrier property and an elastomer layer having a high flexibility has been proposed.

An example of a material having excellent fuel barrier properties is a fluororesin. However, fluororesin has inherently low adhesive strength, and it is difficult to directly bond fluororesin and other materials (base materials). Even if there is a certain level of adhesive strength, the adhesive strength tends to vary depending on the type of substrate, and the reliability of adhesiveness is often insufficient.

As a method of bonding fluororesin and other materials: A method of physically roughing the surface of the substrate by sandblasting, etc.,
2. A method of surface treatment of fluororesin such as sodium etching, plasma treatment, photochemical treatment,
3. A method of bonding using an adhesive,
Etc. are mainly considered.

However, the above processes 1 and 2 require a processing step, and the process is complicated and the productivity is poor. Moreover, the kind and shape of a base material are limited. In the first place, the adhesive strength is insufficient, and problems (coloring and scratches) on the appearance of the obtained laminate are likely to occur.

Various studies on the adhesive of the above 3 have been conducted. General hydrocarbon adhesives have inadequate adhesion and inadequate heat resistance, and can withstand the adhesive conditions of fluoropolymers that generally require molding and processing at high temperatures. It causes peeling and coloring due to decomposition. Since the laminate using this adhesive also has insufficient heat resistance, chemical resistance and water resistance of the adhesive layer, the adhesive force cannot be maintained due to temperature change or environmental change, and lacks reliability.

On the other hand, studies on adhesion using an adhesive or an adhesive composition using a fluororesin having a functional group have been conducted. For example, a fluororesin obtained by graft polymerization of a hydrocarbon monomer having a carboxyl group, carboxylic anhydride residue, epoxy group or hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane on the fluororesin Fluorine-containing copolymers obtained by copolymerization of tetrafluoroethylene and chlorotrifluoroethylene with reports on adhesives (for example, Patent Documents 1 to 6) and hydrocarbon monomers containing a functional group such as hydroxyl alkyl vinyl ether And a report of using an adhesive composition of an ethylene / tetrafluoroethylene polymer (hereinafter also referred to as ETFE) cured with vinyl chloride and a corona discharge treatment by curing an adhesive composition with an isocyanate curing agent (for example, Patent Document 7) ) Has been made. These adhesives or adhesive compositions using a fluorine-containing polymer obtained by graft polymerization or copolymerization of a hydrocarbon-based functional group monomer have insufficient heat resistance and are processed at a high temperature with a fluororesin. During use, decomposition, foaming, etc. occur, reducing the adhesive strength, peeling off, or coloring. In the adhesive composition described in Patent Document 7, the fluororesin requires corona discharge treatment.

Moreover, what used the fluorine-containing polymer which has a functional group which copolymerized the perfluoro vinyl ether compound containing a carboxylic acid or its derivative with the fluorine-containing monomer for the adhesive agent or adhesive composition is reported. Patent Document 8 describes a laminate using a fluororesin having a functional group introduced by copolymerizing perfluorovinyl ether having a carboxylic acid group or a derivative thereof with tetrafluoroethylene or the like. This is a laminate of the above fluoropolymer having a carboxylic acid group or the like on a metal or other substrate through an adhesive resin such as an epoxy resin or a urethane resin, and directly adheres to a metal, glass or other resin. However, there are problems in heat resistance, chemical resistance, and solvent resistance of epoxy resin and urethane resin during use. In addition, although bonding is possible through an epoxy resin or a urethane resin, a method for directly bonding to metal, glass, or other resin is not specified.

Patent Document 9 reports a technique of laminating a synthetic resin layer and an elastomer layer, but it is necessary to blend a specific type of elastomer into the elastomer layer.

JP-A-7-18035 Japanese Patent Application Laid-Open No. 7-259592 Japanese Patent Laid-Open No. 7-25594 JP 7-173230 A JP-A-7-173446 JP-A-7-173447 Japanese Unexamined Patent Publication No. 7-228848 US Pat. No. 4,916,020 Japanese Patent No. 2987391

The present invention provides a fluororesin composition that is excellent in adhesiveness to an elastomer, has a relatively large MFR, is excellent in moldability, and does not cause foaming even during high-temperature processing. The present invention also provides a laminate having a high fuel barrier property and flexibility and in which a fluororesin layer and an elastomer layer are firmly bonded.

The present invention includes a fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer, and an aromatic asymmetric polyfunctional compound. ,
The aromatic asymmetric polyfunctional compound relates to a fluororesin composition characterized by being 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the fluororesin.

Furthermore, the aromatic asymmetric polyfunctional compound preferably has a fluorine atom.

Furthermore, it is preferable that fluororubber is included.

Further, the fluororesin is selected from the group consisting of a copolymer composed of tetrafluoroethylene and hexafluoropropylene, a copolymer composed of ethylene and tetrafluoroethylene, and a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene. It is preferable that there is at least one.

This invention relates also to the laminated body characterized by including the fluororesin layer (a) formed from the said fluororesin composition, and the elastomer layer (b) formed from an elastomer composition.

Further, the elastomer composition includes acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber. And at least one elastomer selected from the group consisting of acrylic rubbers.

Furthermore, the elastomer composition preferably contains at least one compound selected from the group consisting of onium salts, amine compounds and epoxy resins.

The present invention also relates to a molded article formed from the laminate.

The present invention also relates to a fuel tube formed from the laminate.

The present invention also relates to a method for manufacturing the laminate.

The present invention is described in detail below.

The fluororesin inherently has low adhesive strength, and it is difficult to directly bond the fluororesin and other materials. However, according to the knowledge of the present inventors, if the fluororesin layer is formed from a fluororesin composition containing a fluororesin having a specific functional group and a polyfunctional compound, the elastomer layer formed from the elastomer composition Can be bonded with high adhesive strength.

However, when a symmetric polyfunctional compound is added to a fluororesin having a specific functional group, the MFR of the fluororesin is greatly reduced and the extrusion speed during molding is reduced (the MFR is reduced to less than 0.2, It has been found that the moldability at the time of melt molding is extremely reduced) and that foaming is likely to occur at the time of molding at a high temperature.

Therefore, as a result of earnestly examining the means for solving this problem, the present inventors, in the fluororesin composition containing a fluororesin having a specific functional group, has an aromatic ring among polyfunctional compounds, and It has been found that the use of a polyfunctional compound having an asymmetric structure can prevent the MFR from being lowered and foaming during molding.

That is, the fluororesin composition of the present invention comprises a fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer and an aromatic asymmetric polymorph. And a functional compound.

In the fluororesin composition of the present invention, the fluororesin and the aromatic asymmetric polyfunctional compound may be present alone without bonding with each other, or the respective functional groups react with each other. Depending on the situation, they may exist in combination with each other, or may exist in combination with those existing alone.

The aromatic asymmetric polyfunctional compound is an organic compound having one or more aromatic rings in one molecule and having two or more functional groups of the same or different types, and is asymmetric (unsymmetrical). ) A compound having a structure. Even if the functional groups possessed by the compounds having an asymmetric structure are of the same type, the reactivity differs from each other due to the difference in the bonding position in the molecule. N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-diaminodiphenyl ether [4,4′-DPE], 2,2-bis [4- (4-aminophenoxy) phenyl] propane [BAPP ], 2,2-bis (4-hydroxyphenyl) perfluoropropane [bisphenol AF] and the like are compounds having an aromatic ring and having two or more amino groups or hydroxyl groups, but are symmetrical polyfunctional It is a compound and is not included in the aromatic asymmetric polyfunctional compound.

The functional group possessed by the aromatic asymmetric polyfunctional compound generally has reactivity such as carbonyl group, carboxyl group, haloformyl group, amide group, olefin group, amino group, isocyanate group, hydroxy group, epoxy group, etc. Are known functional groups. The compound having these functional groups is expected not only to have high affinity with the elastomer, but also to react with the functional groups of the fluororesin and further improve the adhesion.

Examples of the aromatic asymmetric polyfunctional compound include 3,4′-diaminodiphenyl ether [3,4′-DPE], 2,4,4′-triaminodiphenyl ether [TADE], 2,3′-diaminodiphenyl ether [ 2,3′-DPE], 2,5-bis (4-aminophenoxy) -biphenyl [P-TPE-Q], the following formula

2,2-bis (3,4'-hydroxyphenyl) perfluoropropane represented by the following general formulas (1) to (3)

(In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group, and when having a plurality of R ^{1 s} , they may be the same or different.)
And a diamine compound represented by the following general formula (4):

(In the formula, each R ² is the same or different and represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, and at least one of the four R ² is fluoroalkyl. Group.)
It is preferable that it is at least 1 sort (s) selected from the group which consists of diamine compound represented by these.

Examples of the diamine compound represented by the general formulas (1) to (3) include 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene [TMBAB] and the like. Examples of the diamine compound represented by (4) include 4,4′-diamino-2- (trifluoromethyl) diphenyl ether [TFDPE].

The aromatic asymmetric polyfunctional compound preferably has a fluorine atom bonded to a carbon atom, more preferably has a fluoroalkyl group or a fluorophenyl group, from the viewpoint of excellent affinity with a fluororesin. , 2-bis (3,4'-hydroxyphenyl) perfluoropropane and at least one selected from the group consisting of diamine compounds represented by the general formulas (1) to (4) are more preferable. Particularly preferred is at least one selected from the group consisting of TMBAB and TFDPE. When the aromatic asymmetric polyfunctional compound is a compound having a fluorine atom, the amount of the polyfunctional compound used can be reduced without impairing the adhesive strength with the elastomer.

The aromatic asymmetric polyfunctional compound is 0.05 to 10.0 parts by mass and preferably 0.06 to 5.0 parts by mass with respect to 100 parts by mass of the fluororesin. If the amount of the aromatic asymmetric polyfunctional compound is too small, sufficient adhesive strength tends to be not obtained when laminated with the elastomer, and if too large, the dispersibility in the fluororesin is deteriorated and the molded product machine There is a tendency for physical properties to deteriorate and foaming to occur during molding.

The fluororesin has at least one functional group selected from the group consisting of a carbonyl group, an olefin group, and an amino group at the main chain end or side chain end of the polymer. When the fluororesin has these functional groups, adhesion to the elastomer is improved.

A carbonyl group is a functional group having —C (═O) —.

Specifically, for example,
Carbonate group [—O—C (═O) —OR ³ (wherein R ³ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) ],
A haloformyl group [—C (═O) X ¹ , X ¹ is a halogen atom],
Formyl group [—C (═O) H],
Formula: —R ⁴ —C (═O) —R ⁵ (wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent group having 1 to 20 carbon atoms. An organic group of
Formula: —O—C (═O) —R ⁶ (wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) A group represented by
Carboxyl group [—C (═O) OH],
An alkoxycarbonyl group [—C (═O) OR ⁷ (wherein R ⁷ is a monovalent organic group having 1 to 20 carbon atoms)],
Carbamoyl group [—C (═O) NR ⁸ R ⁹ (wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) )],
Acid anhydride bond [—C (═O) —O—C (═O) —],
An isocyanate group [—N═C═O],
Etc.

Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ⁴ include a methylene group, —CF ₂ — group, —C ₆ H ₄ — group, and specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group. Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like. Specific examples of R ⁸ and R ⁹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

Among these carbonyl groups, at least one selected from the group consisting of a carboxyl group, a haloformyl group, an alkoxycarbonyl group, and a carbonate group from the viewpoint of ease of introduction into a fluororesin and reactivity with other materials. And at least one selected from the group consisting of —COOH, —OC (═O) OCH ₂ CH ₂ CH ₃ , —COF, and —OC (═O) OCH (CH ₃ ) _2. More preferably.

An olefin group is a functional group having a carbon-carbon double bond. As the olefin group, the following formula:
-CR ¹⁰ = CR ¹¹ R ¹²
(Wherein R ¹⁰ , R ¹¹ and R ¹² may be the same or different and are a hydrogen atom, a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms). functional group can be mentioned _{that, -CF = CF 2, -CH =} CF 2, it is preferably at least one -CF = CHF, selected from the group consisting of -CF = CH ₂ and -CH = CH ₂ .

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. As an amino group, the following formula:
-NR ¹³ R ¹⁴
(Wherein, R ¹³ and R ¹⁴ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). , —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , and —NH (C ₆ H ₅ ) It is preferably at least one selected from the group consisting of

The number of terminal groups of the fluororesin can be measured by the methods described in JP-B-37-3127 and WO99 / 45044. For example, when an infrared absorption spectrum analysis of a fluororesin film sheet is performed using an infrared spectrophotometer and the number of functional groups is measured from an absorption band having a frequency specific to the functional group, for example, the —COF terminal is 1884 cm ^{− 1} absorption bands, -COOH ends are absorption bands of 1813 cm ^-1 and 1775 cm ^-1 , -COOCH ₃ ends are absorption bands of 1795 cm ^-1 , -CONH ₂ ends are absorption bands of 3438 cm ^-1 , -CH ₂ OH ends are The absorption band at 3648 cm ^−1, the —CF═CF ₂ end can be calculated from the absorption band at 1790 cm ⁻¹ .

The method for introducing the functional group into the fluororesin is not particularly limited. For example, a method of copolymerizing a monomer having the functional group at the time of fluororesin polymerization, the functional group or a functional group that can be converted to the functional group. A method of polymerizing using a polymerization initiator having a polymer, a method of introducing the above functional group into a fluororesin by a polymer reaction, a method of thermally decomposing a polymer main chain in the presence of oxygen, a strong shear force such as a twin screw extruder And a method for converting the terminal of the fluororesin using a device capable of adding.

Monomers having the above functional groups include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, citraconic anhydride, mesaconic acid And aliphatic unsaturated carboxylic acids such as mesaconic anhydride, aconitic acid, and aconitic anhydride.

The number of functional groups of the fluororesin is preferably 20 to 5000 per 1 million carbon atoms constituting the fluororesin, more preferably 30 to 4000, and 40 to 3000. Further preferred. When the number is less than 20, the adhesive strength with the elastomer tends to decrease, and when the number exceeds 5000, foaming tends to occur in the molded product.

The fluororesin having the functional group used in the present invention is not only composed of molecules having the functional group at one end, both ends or side chains of the main chain in one polymer, It may be a mixture of a molecule having the functional group at one end, both ends or side chains of the main chain, and a molecule not containing the functional group.

Although it does not specifically limit as said fluororesin, It is preferable that it is a fluororesin containing at least 1 type of fluorine-containing ethylenic polymer. The fluorinated ethylenic polymer preferably has a structural unit derived from at least one fluorinated ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene [TFE], formula (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
One or more perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: chlorotrifluoroethylene [CTFE], trifluoroethylene, hexafluoroisobutene, vinylidene fluoride [VdF], vinyl fluoride Equation (6):
^{_{CH 2 = CX 2 (CF 2}} ) n X 3 (6)
(In the formula, X ² represents a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10.)
And the like.

The fluororesin may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Examples of such a monomer include those other than the fluoroolefin and perfluoroolefin. Non-fluorine ethylenic monomers can be mentioned. Examples of the non-fluorine ethylenic monomer include ethylene, propylene, and alkyl vinyl ethers. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

The fluororesin is easy to mold the fluororesin composition, and the resulting molded product has excellent heat resistance, chemical resistance and oil resistance.
(1) Ethylene / TFE copolymer consisting of ethylene and TFE [ETFE]
(2) TFE and equation (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
A copolymer comprising one or more perfluoroethylenically unsaturated compounds represented by the formula, for example, a copolymer [PFA] comprising TFE and perfluoro (alkyl vinyl ether) [PAVE] or TFE and hexafluoropropylene Copolymer comprising [HFP] [FEP]
(3) TFE, ethylene and formula (5):
CF ₂ = CF-R _f ¹ (5)
(Wherein, R _f ¹ is —CF ₃ or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). Ethylene-TFE-HFP copolymer, ethylene-TFE-perfluoroethylenically unsaturated compound copolymer (4) polyvinylidene fluoride [PVDF]
(5) Copolymer comprising CTFE and TFE [CTFE / TFE copolymer]
It is preferable that it is either.

The fluororesin is preferably at least one selected from the group consisting of ETFE, CTFE / TFE copolymer, PFA and FEP, and is selected from the group consisting of ETFE, CTFE / TFE copolymer and FEP. More preferably, it is at least one kind.

ETFE
ETFE is preferable in terms of improving mechanical properties and fuel barrier properties. The content molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 37:63 to 85:15, and still more preferably 38:62 to 80:20.

ETFE may be a copolymer composed of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene. As the copolymerizable monomer, the following formulas CH ₂ = CX ⁴ R _f ³ , CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ , CH ₂ = C (R _f ³ ) ₂
(Wherein, X ⁴ represents a hydrogen atom or a fluorine atom, and R _f ³ represents a fluoroalkyl group which may contain an etheric oxygen atom)
Among them, a fluorine-containing vinyl monomer represented by CH ₂ = CX ⁴ R _f ³ is preferable, and CH ₂ in which R _f ³ is a fluoroalkyl group having 1 to 8 carbon atoms. The fluorine-containing vinyl monomer represented by = CX ⁴ R _f ³ is more preferable.

Specific examples of the fluorine-containing vinyl monomer represented by the above formula include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,5-trihydroperfluoropentene-1. 1,1,7-trihydroperfluoroheptene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1,2,2,3 3,4,4,5,5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluorobutene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene _(CH 2 = CFC ₂ CF ₂ CF ₂ H), and the like.

The monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride described above.

The monomer copolymerizable with TFE and ethylene is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, and more preferably 0.2 to 4 mol% with respect to the fluorine-containing ethylenic polymer. Is particularly preferred.

CTFE / TFE copolymer The CTFE / TFE copolymer preferably has a CTFE / TFE unit molar ratio of CTFE: TFE = 2: 98 to 98: 2 and 5:95 to 90:10. It is more preferable. If the CTFE unit is less than 2 mol%, the chemical permeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

CTFE / TFE copolymer, CTFE, TFE, and may be a copolymer comprising CTFE and TFE monomer copolymerizable with _{ethylene, VdF, HFP, CF 2 =} CF-OR f 4 (Wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Represented by perfluoro (alkyl vinyl ether) [PAVE], CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (Wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10) And a vinyl monomer represented by CF ₂ ═CF—OCH ₂ —Rf ⁵ (wherein Rf ⁵ represents a perfluoroalkyl group having 1 to ⁵ carbon atoms). Perfluorovinyl Examples include ether derivatives, among which PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

The CTFE / TFE copolymer has a monomer unit derived from CTFE and a monomer copolymerizable with TFE in an amount of 0.1 to 10 mol%, and a total of CTFE units and TFE units of 90 to 99.99. It is preferably 9 mol%. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

FEP
FEP is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as FEP, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of HFP units, 80-97 mol% of TFE units, and 3-20 mol% of HFP units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

FEP may be a copolymer comprising TFE, HFP, and a monomer copolymerizable with TFE and HFP, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. As the monomer, perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—OR _f ⁴ (wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). , CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, fluorine represents an atom or a chlorine atom, n represents a vinyl monomer represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is 1 to carbon atoms 5 represents a perfluoroalkyl group, and the like. Among them, PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

FEP has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and 90 to 99.9 mol% of TFE units and HFP units in total. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

PFA
PFA is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as PFA, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of PAVE units, 80-97 mol% of TFE units, and 3-20 mol% of PAVE units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE, and even more preferably PMVE.

PFA may be a copolymer composed of TFE, PAVE, and a monomer copolymerizable with TFE and PAVE, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. HFP, CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, represents a fluorine atom or a chlorine atom, a vinyl monomer n is represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is C 1 -C An alkyl perfluorovinyl ether derivative represented by ˜5).

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of TFE unit and PAVE unit is 90 to 99.9 mol%. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

The melting point of the fluororesin is preferably 150 to 340 ° C, more preferably 150 to 330 ° C, and further preferably 170 to 320 ° C. If the melting point of the fluororesin is less than 150 ° C., the heat resistance tends to decrease. There is a tendency not to express.

The fluororesin preferably has a fuel permeation coefficient of 20 (g · mm) / (m ² · day) or less, and 15 (g · mm) / (m ² · day) or less. More preferably, it is more preferably 10 (g · mm) / (m ² · day) or less, and particularly preferably 5 (g · mm) / (m ² · day) or less. The lower limit value of the fuel permeability coefficient is not particularly limited, and the lower the value, the better. When the fuel permeation coefficient exceeds 20 (g · mm) / (m ² · day), the fuel permeation resistance is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product. Economically unfavorable. Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability. On the other hand, when the fuel permeation coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

The fuel permeability coefficient is measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method defined in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. Put 18 mL, and set the sheet-like test piece in the container open part and seal it to make a test body. The test specimen is placed in a thermostatic device (60 ° C.), the weight of the test specimen is measured, and when the weight loss per unit time becomes constant, the fuel permeability is obtained by the following formula.

Although it does not specifically limit as a manufacturing method of the said fluororesin, The method as described in Unexamined-Japanese-Patent No. 2005-298702, international publication 2005/100420 pamphlet, etc. can be mention | raise | lifted.

The fluororesin composition of the present invention preferably further contains fluororubber.

Examples of the fluororubber include perfluorofluororubber, non-perfluorofluororubber, fluorine-containing thermoplastic elastomer, and the like, which may be crosslinked or uncrosslinked.

Examples of the perfluorofluororubber include a TFE / PAVE copolymer and a TFE / HFP / PAVE copolymer.

Examples of the non-perfluorofluororubber include VdF polymers and TFE / propylene copolymers, which can be used alone or in any combination within a range not impairing the effects of the present invention. .

Moreover, what was illustrated as said perfluoro fluororubber or non-perfluoro fluororubber is the structure of a main monomer, and what copolymerized the monomer which gives a bridge | crosslinking site | part, a modified monomer, etc. can be used suitably. Monomers and modifying monomers that give a crosslinking site include monomers that give known crosslinking sites such as those containing iodine, bromine, and double bonds, transfer agents, and modifications such as known ethylenically unsaturated compounds. Monomers and the like can be used.

Specific examples of the VdF-based polymer include a VdF / HFP copolymer, a VdF / TFE / HFP copolymer, a VdF / TFE / propylene copolymer, a VdF / ethylene / HFP copolymer, and a VdF / TFE copolymer. / PAVE copolymer, VdF / PAVE copolymer, VdF / CTFE copolymer, and the like. More specifically, it is preferably a fluorine-containing copolymer composed of 25 to 85 mol% of VdF and 75 to 15 mol% of at least one other monomer copolymerizable with VdF, more preferably , A fluorine-containing copolymer comprising 40 to 80 mol% of VdF and 60 to 20 mol% of at least one other monomer copolymerizable with VdF.

Here, as at least one other monomer copolymerizable with VdF, for example, TFE, CTFE, trifluoroethylene, HFP, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetra Examples thereof include fluorine-containing monomers such as fluoroisobutene, PAVE and vinyl fluoride, and non-fluorine monomers such as ethylene, propylene and alkyl vinyl ether. These can be used alone or in any combination.

Among the fluororubbers, a fluororubber containing VdF units is preferable from the viewpoint of heat resistance, compression set, workability, and cost, and fluorine having VdF units and HFP units is preferable from the viewpoint of good compression set. More preferably, it is rubber.

Further, it is preferably at least one rubber selected from the group consisting of VdF / HFP fluororubber, VdF / TFE / HFP fluororubber, and TFE / propylene fluororubber, more preferably VdF / TFE / HFP fluororubber. preferable.

Perfluoro fluorine rubber and non-perfluoro fluorine rubber can be produced by a usual emulsion polymerization method. What is necessary is just to determine suitably polymerization conditions, such as temperature at the time of superposition | polymerization, time, according to the kind of monomer, and the objective rubber | gum.

The fluorine-containing thermoplastic elastomer is not particularly limited, and comprises at least one elastomeric polymer segment and at least one non-elastomeric polymer segment, and the elastomeric polymer segment and the non-elastomeric polymer. It is preferable that at least one of the segments is a fluorine-containing polymer segment.

The elastomeric polymer segment is a segment that imparts flexibility to the polymer, and the glass transition point is preferably 25 ° C. or less, and more preferably 0 ° C. or less. Examples of the structural unit include TFE, CTFE, HFP, and general formula:
^{_{CF 2 = CFO (CF 2 CFX}} 4 O) p - (CF 2 CF 2 CF 2 O) q -R f 6
(In the formula, X ⁴ is a fluorine atom or —CF ₃ , R _f ⁶ is a C 1-5 perfluoroalkyl group, p is an integer of 0-5, and q is an integer of 0-5. )
Perhaloolefins such as perfluorovinyl ether represented by: Fluorine-containing monomers such as VdF, trifluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride; Non-fluorine monomers such as ethylene, propylene, and alkyl vinyl ethers.

As a monomer which gives a crosslinking site, for example, a general formula:
CX ⁵ ₂ = CX ⁵ -R _f ⁷ CHR ¹⁵ X ⁶
(In the formula, X ⁵ represents a hydrogen atom, a fluorine atom or —CH ₃ , R _f ⁷ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoropolyoxyalkylene group, and R ¹⁵ represents a hydrogen atom. Atom or —CH ₃ , X ⁶ is an iodine atom or a bromine atom)
Iodine or bromine-containing monomer represented by the general formula:
_{CF 2 = CFO (CF 2 CF} (CF 3) O) m (CF 2) n -X 7
(In the formula, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁷ is a cyano group, a carboxyl group, an alkoxycarbonyl group or a bromine atom)
And the like, and these can be used alone or in any combination.

As structural units of the non-elastomeric polymer segment, TFE, CTFE, PAVE, HFP, general formula:
CF ₂ = CF (CF ₂ ) _r X ⁸
(Wherein r is an integer of 1 to 10 and X ⁸ is a fluorine atom or a chlorine atom)
Perhaloolefins such as perfluoro-2-butene; VdF, vinyl fluoride, trifluoroethylene, general formula:
^{_{CH 2 = CX 9 - (CF}} 2) s -X 9
(Wherein X ⁹ is a hydrogen atom or a fluorine atom, and s is an integer of 1 to 10)
A partially fluorinated olefin such as CH ₂ ═C (CF ₃ ) ₂ ; a non-fluorine monomer such as ethylene, propylene, vinyl chloride, vinyl ether, vinyl carboxylate, and acrylic acid. it can.

Among these, a fluorine-containing thermoplastic elastomer in which the elastomeric polymer segment is a TFE / VdF / HFP copolymer and the non-elastomeric polymer segment is a TFE / ethylene copolymer is preferable. The flexible polymer segment is TFE / VdF / HFP = 0-35 / 40-90 / 5-50 mol%, and the non-elastomeric polymer segment is TFE / ethylene = 20-80 / 80-20 mol%. A fluorine-containing thermoplastic elastomer is more preferable.

The fluorine-containing thermoplastic elastomer is preferably a fluorine-containing multi-segmented polymer in which an elastomeric polymer segment and a non-elastomeric polymer segment are bonded in the form of a block or graft in one molecule, and the fluorine-containing thermoplastic elastomer is 1 It is preferable that it consists of a triblock polymer consisting of one elastomeric polymer segment and two non-elastomeric polymer segments, at least one of which is a fluorine-containing polymer segment.

As the fluorine-containing thermoplastic elastomer, various known methods can be adopted to connect the elastomeric polymer segment and the non-elastomeric polymer segment in the form of a block or graft to form a fluorine-containing multi-segmented polymer. However, a method for producing a block-type fluorine-containing multi-segmented polymer disclosed in JP-B-58-4728, a method for producing a graft-type fluorine-containing multi-segmented polymer disclosed in JP-A-62-34324, etc. Can be preferably employed.

In particular, since the segmentation rate (blocking rate) is high and a homogeneous and regular segmented polymer can be obtained, Japanese Patent Publication No. 58-4728, collection of polymer articles (Vol. 49, No. 10, 1992). A block-type fluorine-containing multi-segmented polymer synthesized by the so-called iodine transfer polymerization method described above is preferred.

As a preferable production method of the fluorine-containing thermoplastic elastomer, a known iodine transfer polymerization method can be given as a production method of the fluororubber. For example, the perhaloolefin and, if necessary, a monomer that provides a curing site are stirred under pressure in an aqueous medium in the presence of an iodine compound, preferably a diiodine compound, substantially in the absence of oxygen. However, a method of carrying out emulsion polymerization in the presence of a radical initiator can be mentioned. As a typical example of the iodine compound to be used, for example, a general formula:
R ¹⁶ I _x Br _y
(Wherein x and y are each an integer of 0 to 2 and satisfy 1 ≦ x + y ≦ 2, and R ¹⁶ represents a saturated or unsaturated fluorohydrocarbon group having 1 to ¹⁶ carbon atoms or chlorofluoro A hydrocarbon group or a hydrocarbon group having 1 to 3 carbon atoms, which may contain an oxygen atom)
It can be obtained by the presence of a compound represented by: The iodine or bromine thus introduced functions as a crosslinking point.

Examples of the iodine compound include 1,3-diiodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloro. Perfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, 1,2- diiodoethane, 1,3-diiodo -n- _{propane, CF 2 Br 2, BrCF 2} CF 2 Br, CF 3 CFBrCF 2 Br, CFClBr 2, BrCF 2 CFClBr, CFBrClCFClBr, BrCF 2 CF 2 CF 2 Br, BrCF 2 CFBrOCF 3 1-bromo-2-iodo -Fluoroethane, 1-bromo-3-iodoperfluoropropane, 1-bromo-4-iodoperfluorobutane, 2-bromo-3-iodoperfluorobutane, 3-bromo-4-iodoperfluorobutene-1, 2- Bromo-4-iodoperfluorobutene-1, monoiodomonobromo-substitution, diiodomonobromo-substitution of benzene, (2-iodoethyl) and (2-bromoethyl) -substitution, and the like. These may be used alone or in combination with each other.

Among these, it is preferable to use 1,4-diiodoperfluorobutane, diiodomethane, etc. from the viewpoints of polymerization reactivity, crosslinking reactivity, availability, and the like.

The radical polymerization initiator used in the present invention may be the same as that conventionally used for the polymerization of fluorine-containing elastomers. These initiators include organic and inorganic peroxides and azo compounds. Typical initiators include persulfates, carbonate peroxides, peroxide esters and the like, and a preferred initiator is ammonium persulfate (APS). APS may be used alone or in combination with a reducing agent such as sulfites and sulfites.

A wide range of emulsifiers can be used as the emulsion polymerization. From the viewpoint of suppressing the chain transfer reaction to the emulsifier molecule that occurs during the polymerization, the carboxylic acid having a fluorocarbon chain or a fluoropolyether chain is used. Salts are desirable. The amount of the emulsifier used is preferably about 0.05 to 2% by mass, and particularly preferably 0.2 to 1.5% by mass of the added water.

The polymerization pressure can be varied within a wide range. Generally, it is the range of 0.5-5 MPa. The higher the polymerization pressure, the higher the polymerization rate. Therefore, from the viewpoint of improving productivity, the polymerization pressure is preferably 0.8 MPa or more.

When an elastomeric polymer segment of a fluorine-containing thermoplastic elastomer is produced by the above iodine transfer polymerization method, the number average molecular weight of the fluorine-containing multi-segmented polymer obtained is imparted with flexibility, elasticity, mechanical properties. From the point of provision, it is preferably 3,000 to 750,000, and more preferably 5,000 to 300,000.

The terminal portion of the elastomeric polymer segment thus obtained is a perhalo type, and has an iodine atom that serves as a starting point for block copolymerization of the non-elastomeric polymer segment.

The block copolymerization of the non-elastomeric polymer segment to the elastomeric polymer segment can then be carried out by changing the monomer for the non-elastomeric polymer segment following the emulsion polymerization of the elastomeric polymer segment.

The number average molecular weight of the obtained non-elastomeric polymer segment is preferably 1,000 to 1,200,000, more preferably 3, from the viewpoint of imparting heat resistance to the fluororesin composition and imparting mechanical properties. 000 to 600,000.

Further, in the fluorine-containing thermoplastic elastomer, the polymer molecule of only the elastomeric polymer segment to which the non-elastomeric polymer segment is not bonded is 20% by mass with respect to the total amount of the segment and the polymer molecule in the fluorine-containing thermoplastic elastomer. Or less, more preferably 10% by mass or less.

The fluororubber is preferably a cross-linked cross-linked fluoro rubber. The crosslinked fluororubber is a molded article formed from a fluororesin composition or a later-described product, which is obtained by dynamically crosslinking an uncrosslinked fluororubber under melting conditions in the presence of the fluororesin and a crosslinking agent. It is preferable because the flexibility of the fluororesin layer (a) is improved. In this case, the tensile modulus of the laminate of the present invention described later can be 300 MPa or less. It is also possible to improve the adhesion to the elastomer.

Here, the dynamic crosslinking treatment refers to dynamically crosslinking uncrosslinked fluororubber simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an extruder, or the like. Among these, an extruder such as a twin screw extruder is preferable because a high shear force can be applied. By dynamically crosslinking, the phase structure of the fluororesin and the crosslinked fluororubber can be controlled.

In addition, the melting condition means that the temperature is equal to or higher than the temperature at which the fluororesin melts. The suitable temperature range varies depending on the melting point of the fluororesin and the glass transition temperature of the uncrosslinked fluororubber, but is preferably 120 to 330 ° C, and more preferably 130 to 320 ° C. If the temperature is less than 120 ° C, the dispersion between the fluororesin and the fluororubber tends to be coarsened, and if it exceeds 330 ° C, the fluororubber tends to be thermally deteriorated.

The obtained fluororesin composition can have a structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber forms a dispersed phase, or the fluororesin and the cross-linked fluororubber form a co-continuity. Of these, the fluororesin preferably has a structure in which a continuous phase is formed and the cross-linked fluororubber forms a dispersed phase.

Even when the uncrosslinked fluororubber initially forms a matrix, as the crosslinking reaction proceeds, the uncrosslinked fluororubber becomes a crosslinked fluororubber and the melt viscosity increases, and the crosslinked fluororubber becomes a dispersed phase. Or form a co-continuous structure with the fluororesin.

Further, the fluororesin composition may include a co-continuous structure of the fluororesin and the cross-linked fluororubber in a part of the structure in which the fluororesin forms a continuous phase and the cross-linked fluororubber forms a dispersed phase. .

When such a structure is formed, when a fluororesin composition is molded, a molded product having excellent fuel barrier properties, heat resistance, chemical resistance and oil resistance and having good moldability can be obtained. The average dispersed particle size of the cross-linked fluororubber is preferably 0.01 to 30 μm, more preferably 0.1 to 20 μm, and further preferably 0.1 to 10 μm. If the average dispersed particle size is less than 0.01 μm, the fluidity tends to decrease, and if it exceeds 30 μm, the strength of the molded product tends to decrease.

The fluorine concentration of the crosslinked fluororubber is preferably 68% by mass or more, more preferably 68 to 75% by mass, further preferably 69 to 74% by mass, and 70 to 73% by mass. Is particularly preferred. When the fluorine concentration is less than 68% by mass, the fuel barrier property tends to decrease.

The crosslinking agent used for the dynamic crosslinking treatment can be appropriately selected according to the type of fluororubber and the melt-kneading conditions.

The cross-linking system used for the dynamic cross-linking treatment is a perfluoro fluoro rubber, a non-perfluoro fluoro rubber, or a fluorine-containing thermoplastic elastomer containing a cross-linkable group (cure site). What is necessary is just to select suitably according to the use of a molded article.

As the crosslinking system, any of a polyol crosslinking system, an organic peroxide crosslinking system, and a polyamine crosslinking system can be employed.

Here, crosslinking by a polyol crosslinking system is preferable in that it has a carbon-oxygen bond at the crosslinking point, has a small compression set, and has good moldability.

When crosslinked by an organic peroxide crosslinking system, since it has a carbon-carbon bond at the crosslinking point, a polyol crosslinking system having a carbon-oxygen bond at the crosslinking point and a polyamine having a carbon-nitrogen double bond Compared to the cross-linking system, it is characterized by excellent chemical resistance and steam resistance.

When crosslinked by polyamine crosslinking, it has a carbon-nitrogen double bond at the crosslinking point and is characterized by excellent dynamic mechanical properties. However, compression set tends to increase as compared with the case of crosslinking using a polyol crosslinking system or an organic peroxide crosslinking system.

Therefore, it is preferable to use a polyol crosslinking system or an organic peroxide crosslinking system, and it is more preferable to use a polyol crosslinking system for the dynamic crosslinking treatment.

The crosslinking agent used for the dynamic crosslinking treatment is preferably at least one selected from the group consisting of organic peroxides, polyamine compounds and polyhydroxy compounds.

Examples of the polyamine compound include polyamine compounds such as hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, and 4,4′-bis (aminocyclohexyl) methanecarbamate. Among these, N, N′-dicinnamylidene-1,6-hexamethylenediamine is preferable.

As the polyhydroxy compound, a compound conventionally known as a cross-linking agent for fluororubber can be used, and in particular, a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.

The polyhydroxy aromatic compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2-bis (4-hydroxyphenyl) perfluoropropane. (Hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4 ′ -Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2 , 2-Bis (4-hydroxyphenyl) Tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 Examples include ', 5,5'-tetrabromobisphenol A. These polyhydroxy aromatic compounds may be an alkali metal salt, an alkaline earth metal salt or the like, but when the copolymer is coagulated using an acid, it is preferable not to use the metal salt.

The organic peroxide may be an organic peroxide that can easily generate a peroxy radical in the presence of heat or a redox system. For example, 1,1-bis (t-butylperoxy) -3, 5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α-bis (t- Butylperoxy) -p-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne -3, benzoyl peroxide, t-butyl peroxybenzene, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, etc. Can give. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) -hexyne-3 are preferable.

Among these, a polyhydroxy compound is preferable from the viewpoint of small compression set such as a molded article to be obtained and excellent moldability, a polyhydroxy aromatic compound is more preferable because of excellent heat resistance, and bisphenol AF is preferable. Further preferred.

In the polyol crosslinking system, a crosslinking accelerator is usually used in combination with the polyol crosslinking agent. When a crosslinking accelerator is used, the crosslinking reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.

An onium compound is generally used as a crosslinking accelerator for a polyol crosslinking system. The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Of these, quaternary ammonium salts and quaternary phosphonium salts are preferred.

The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5, 4,0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 , 4,0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo 5,4,0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [ 5,4,0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl -1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- ( 3-phenylpropyl) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter referred to as BTPPC), benzyltributylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl. Examples thereof include -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, and among these, benzyltriphenylphosphonium chloride (BTPPC) is preferable from the viewpoint of crosslinkability and physical properties of the crosslinked product.

Further, as a crosslinking accelerator, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can also be used.

Examples of the organic peroxide crosslinking accelerator include triallyl cyanurate, triallyl isocyanurate (TAIC), triacryl formal, triallyl trimellitate, N, N'-m-phenylenebismaleimide, dipropargyl terephthalate. , Diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5 -Triazine-2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N ', N'-tetraallylphthala N, N, N ′, N′-tetraallylmalonamide, trivinylisocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, triallyl phosphite Etc. Among these, triallyl isocyanurate (TAIC) is preferable from the viewpoint of crosslinkability and physical properties of the cross-linked product.

As a compounding quantity of a crosslinking agent, it is preferable that it is 0.1-10 mass parts with respect to a total of 100 mass parts of uncrosslinked fluororubber, More preferably, it is 0.3-5 mass parts. When the crosslinking agent is less than 0.1 parts by mass, the crosslinking of the uncrosslinked fluororubber does not proceed sufficiently and the heat resistance and oil resistance of the resulting molded product tend to be reduced, and exceeds 10 parts by mass. And there exists a tendency for the moldability of a fluororesin composition to fall.

As a compounding quantity of a crosslinking accelerator, it is preferable that it is 0.01-8 mass parts with respect to a total of 100 mass parts of uncrosslinked fluororubber, More preferably, it is 0.02-5 mass parts. When the crosslinking accelerator is less than 0.01 parts by mass, the crosslinking of the uncrosslinked fluororubber does not proceed sufficiently, and the heat resistance and oil resistance of the resulting molded product tend to decrease, and 8 parts by mass When it exceeds, there exists a tendency for the moldability of a fluororesin composition to fall.

In the fluororesin composition of the present invention, the composition ratio between the fluororesin and the cross-linked fluororubber is preferably 10 to 95% by mass of the fluororesin, 90 to 5% by mass of the cross-linked fluororubber, and 20 to 90% by mass of the fluororesin. More preferably, it is 80 to 10% by mass of the crosslinked fluororubber. When the fluororesin is less than 10% by mass, the fuel barrier property of the obtained molded product tends to be deteriorated and the molding processability tends to be lowered, and when it exceeds 95% by mass, the flexibility of the obtained molded product is lowered. Tend.

The fluororesin composition of the present invention comprises other polymers such as polyethylene, polypropylene, polyamide, polyester, polyurethane, inorganic fillers such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate, pigments, Flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc. will affect the effects of the present invention. You may contain in the range which is not.

The melt flow rate (MFR) of the fluororesin composition is preferably 0.2 to 50 g / 10 minutes, and more preferably 1 to 25 g / 10 minutes. If the MFR is less than 0.2 g / 10 min, the fluidity tends to deteriorate and the moldability tends to decrease. Here, MFR shows the value at the time of implementing on the conditions of 297 degreeC and 5000 g load using the Toyo Seiki Seisakusho make melt flow rate measuring device.

Although the method for producing the fluororesin composition of the present invention is not particularly limited, a method in which a fluororesin and a polyfunctional compound are melt-kneaded at a temperature equal to or higher than the melting point of the fluororesin using a Banbury mixer, a pressure kneader, an extruder, or the like, And a method of co-coagulating by adding a polyfunctional compound to an aqueous dispersion containing a fluororesin.

As a method for producing the fluororesin composition of the present invention, a fluororesin, a polyfunctional compound, an uncrosslinked fluororubber, and a cross-linking agent may be used by using a Banbury mixer, a pressure kneader, an extruder, etc. A method of melt-kneading at a melting point or higher is possible. According to this method, a fluororesin composition containing dynamically cross-linked cross-linked fluororubber can be produced. After kneading uncrosslinked fluororubber and a crosslinking agent to obtain a fluororubber composition, the fluororubber composition may be melt-kneaded with a fluororesin and a polyfunctional compound to obtain a fluororesin composition.

This invention is also a laminated body characterized by including the fluororesin layer (a) formed from the said fluororesin composition, and the elastomer layer (b) formed from an elastomer composition.

The elastomer composition includes an elastomer. Examples of the elastomer include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, Ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, silicone rubber, butyl rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, α, β-unsaturated nitrile-conjugated diene copolymer rubber, α, β -Hydride of unsaturated nitrile-conjugated diene copolymer rubber and the like.

The elastomer composition includes acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber and It is preferable to include at least one elastomer selected from the group consisting of acrylic rubber. Among these, the above elastomer composition is composed of acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluororubber, epichlorohydrolin from the viewpoint of heat resistance, oil resistance, weather resistance, and extrusion moldability. More preferably, it comprises at least one elastomer selected from the group consisting of rubber.

The elastomer composition contains at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin from the viewpoint of improving the adhesive strength between the fluororesin layer (a) and the elastomer layer (b). preferable.

The onium salt is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. Among these, quaternary ammonium salts are exemplified. A quaternary phosphonium salt is preferred.

The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5, 4,0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 , 4,0] -7-Undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5,4,0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 , 4,0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5, , 0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5,4 , 0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride (hereinafter also referred to as DBU-B), 8-benzyl-1, 8-diazabicyclo [5,4,0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5,4,0] -7-undecenium chloride, 8- (3-phenylpropylene ) -1,8-diazabicyclo [5,4,0] -7-undecenium chloride, formula (7):

(In the formula, three Rs may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion)
A compound represented by
Formula (8):

(In the formula, n is an integer of 0 to 50)
And a compound of formula (9):

Etc.

Three R in Formula (7) are the same or different, and are a hydrogen atom or a C1-C30 monovalent organic group. Although it does not specifically limit as a C1-C30 monovalent organic group, An aryl group, such as an aliphatic hydrocarbon group and a phenyl group, or a benzyl group is mention | raise | lifted. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁴ ₃ , —C ₂ X ⁴ ₅ , —CH ₂ X ⁴ , —CH ₂ CX ⁴ ₃ , —CH ₂ C ₂ X ⁴ _5, etc., a halogen atom-containing alkyl group having 1 to 30 carbon atoms (X ⁴ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; _benzyl; -C ₆ F _{5, 1~5} phenyl groups or benzyl group hydrogen atoms are substituted with fluorine atoms, such as _{-CH 2 C 6 F 5; -C} 6 H 5-n (CF 3) n A phenyl group or a benzyl group in which 1 to 5 hydrogen atoms are substituted with —CF ₃ such as —CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5). . Formula (10):

As such, it may contain a nitrogen atom.

Among these, DBU-B, or R ¹³ , R ¹⁴ , and R ¹⁵ are alkyl groups having 1 to 20 carbon atoms or the above-mentioned DBU-B from the viewpoint of good adhesion between the fluororesin layer (a) and the elastomer layer (b). Benzyl group, X ⁻ is a monovalent anion, halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), OH ⁻ , RO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , SO ₄ ²⁻ , SO ₃ ²⁻ , SO ₂ ⁻ , RSO ₃ ²⁻ , CO ₃ ²⁻ , NO ₃ ⁻ (R is a monovalent organic group), and the formula (7), the formula (8), and the like are preferable. X ^{− in} (7) is more preferably Cl ⁻ . In formula (8), n is more preferably an integer of 0 to 10, and further preferably an integer of 1 to 5, from the viewpoint of dispersibility when kneaded with rubber.

Among these, in particular, the formula (11):

It is preferable that it is a compound shown by these.

The quaternary phosphonium salt is not particularly limited. For example, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter also referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2. -Methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride and the like can be mentioned, and among these, BTPPC is preferred from the viewpoint of good adhesion between the fluororesin layer (a) and the elastomer layer (b). .

Further, a quaternary ammonium salt, a solid solution of a quaternary phosphonium salt and bisphenol AF, or a compound disclosed in JP-A-11-147891 can also be used.

The blending amount of the onium salt is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. If the amount of the onium salt is less than 0.1 parts by mass, the adhesion between the fluororesin layer (a) and the elastomer layer (b) tends to be insufficient, and if it exceeds 10.0 parts by mass, the elastomer There is a tendency that dispersibility in the composition is deteriorated and mechanical properties of the elastomer layer are lowered.

It does not specifically limit as an amine compound, For example, a hexamethylenediamine carbamate, N, N'- dicinnamylidene-1,6-hexamethylenediamine (henceforth V3), 4,4'-bis (aminocyclohexyl) methanecarbamate Aliphatic polyamine compound derivatives such as 4,4′-diaminodiphenyl ether [4,4′-DPE], 2,2-bis [4- (4-aminophenoxy) phenyl] propane [BAPP], p-phenylenediamine , M-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine, 4,4'-methylenedianiline, dianilinoethane, 4,4'-methylene -Bis (3-nitroaniline), 4,4'-methylene-bis (2-chloroaniline) Emissions), diaminopyridine, an aromatic polyamine compound such as melamine may be used. Among these, V3, 4, 4'-DPE and BAPP are preferable from the viewpoint of good adhesion between the fluororesin layer (a) and the elastomer layer (b).

The compounding amount of the amine compound is preferably 0.1 to 10.0 parts by mass, more preferably 0.2 to 8.0 parts by mass, and 0.3 to 7.0 parts by mass with respect to 100 parts by mass of the elastomer. Further preferred. If the compounding amount of the amine compound is less than 0.1 parts by mass, the adhesion between the fluororesin layer (a) and the elastomer layer (b) tends to be insufficient, and if it exceeds 10.0 parts by mass, the elastomer There is a tendency that dispersibility in the composition is deteriorated and mechanical properties of the elastomer layer are lowered.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and polyfunctional epoxy resin. Among these, as the bisphenol A type epoxy resin, the formula (12):

And the like. Here, in Formula (12), n is preferably 0.1 to 3, more preferably 0.1 to 0.5, and still more preferably 0.1 to 0.3. If n is less than 0.1, the adhesive strength with other materials tends to decrease. On the other hand, when n exceeds 3, the viscosity increases, and uniform dispersion in the rubber tends to be difficult.

0.1-20.0 mass parts is preferable with respect to 100 mass parts of elastomers, the compounding quantity of an epoxy resin has more preferable 0.3-15.0 mass parts, and 0.5-10.0 mass parts is. Further preferred. If the compounding amount of the epoxy resin is less than 0.1 parts by mass, the adhesion between the fluororesin layer (a) and the elastomer layer (b) tends to be insufficient, while the compounding amount of the epoxy resin is 20 When the amount exceeds 0.0 parts by mass, the flexibility of the elastomer layer (b) tends to decrease.

The elastomer contained in the elastomer composition may be an uncrosslinked elastomer or a crosslinked elastomer, but may be an elastomer before crosslinking in terms of excellent adhesion to the layer (a). preferable.

As the crosslinking agent, any crosslinking agent used for ordinary elastomers can be used. For example, sulfur crosslinking agent, peroxide crosslinking agent, polythiol crosslinking agent, quinoid crosslinking agent, resin crosslinking agent, metal oxide, diamine crosslinking agent, polythiols, 2-mercaptoimidazoline, polyol crosslinking agent, There are crosslinking agents such as polyamine crosslinking agents, among which peroxide crosslinking agents, polyol crosslinking agents, polyamine crosslinking agents and the like are preferable from the viewpoint of adhesive properties and mechanical properties of the obtained crosslinked rubber.

As a compounding quantity of the crosslinking agent mix | blended in an elastomer composition, 0.2-10 mass parts is preferable with respect to 100 mass parts of elastomers, and 0.5-8 mass parts is more preferable. If the cross-linking agent is less than 0.2 parts by mass, the cross-linking density tends to be low and compression set tends to be large, and if it exceeds 10 parts by mass, the cross-linking density tends to be too high and tends to break during compression. There is.

In addition, the elastomer composition may contain additives as necessary, for example, fillers, processing aids, plasticizers, colorants, stabilizers, crosslinking aids, adhesion aids, acid acceptors, release agents, and conductivity imparting. Various additives such as additives, thermal conductivity-imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc. can be blended. One or more agents may be blended.

The elastomer composition is an elastomer, an onium salt, an amine compound and / or an epoxy resin, a crosslinking agent, a crosslinking aid, a co-crosslinking agent, a crosslinking accelerator, and other compounding agents such as a filler, which are generally used. It is obtained by kneading using a kneader. As the rubber kneading apparatus, rolls, kneaders, Banbury mixers, internal mixers, twin screw extruders, and the like can be used.

In particular, when a polyol-based crosslinking agent is used as the crosslinking agent, the melting point of the crosslinking agent / crosslinking accelerator is often relatively high, and in order to disperse uniformly in the elastomer composition, the crosslinking agent / crosslinking accelerator is used. A method of kneading while being melted at a high temperature of 120 to 200 ° C. using a closed type kneader such as a kneader and then kneading other compounding agents such as a filler at a relatively low temperature below this is preferable. There is also a method of uniformly dispersing using a solid solution in which a crosslinking agent and a crosslinking accelerator are once melted to lower the melting point.

The crosslinking conditions may be appropriately determined depending on the type of the crosslinking agent to be used. Usually, firing is performed at a temperature of 150 to 300 ° C. for 1 minute to 24 hours.

In addition, as a crosslinking method, a crosslinking reaction is performed under any conditions, not only in a method commonly used such as steam crosslinking, but also under normal pressure, increased pressure, reduced pressure, and in air. be able to.

The manufacturing method of the laminated body of this invention is also one of this invention.

The laminate of the present invention can be produced by laminating a sheet-like fluororesin and a sheet-like elastomer, setting them in a mold, and heat-pressing them. In addition, two layers of a fluororesin composition and an elastomer composition are coextruded by an extruder, or an outer layer is extruded on an inner layer by two extruders to extrude a laminate composed of an inner layer and an outer layer. It can also be produced by extruding and integrating with a machine and then cross-linking.

The configuration of the laminate is not particularly limited. For example, a two-layer configuration including a fluororesin layer (a) and an elastomer layer (b), or a fluororesin layer between two types of the same or different elastomer layers (b). A three-layer structure in which (a) is inserted can be used. It is also possible to further laminate an arbitrary material on the laminate of the present invention.

In order to further improve the adhesion between the fluororesin layer (a) and the elastomer layer (b), the fluororesin may be subjected to a surface treatment as necessary. The type of the surface treatment is not particularly limited as long as it is a treatment method that enables adhesion. For example, discharge treatment such as plasma discharge treatment or corona discharge treatment, wet metal sodium / naphthalene liquid treatment Etc. A primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When the primer treatment is performed, the surface of the fluororesin that has not been surface-treated can be treated, but the surface of the fluororesin that has been previously subjected to plasma discharge treatment, corona discharge treatment, metal sodium / naphthalene liquid treatment, etc. is further primed Processing is more effective.

A molded article formed from the laminate of the present invention is also one aspect of the present invention.

The laminate of the present invention is a laminate having high adhesion strength between layers and having chemical resistance, oil resistance, heat resistance and cold resistance, and is useful as a multilayer fuel tube (hose) or multilayer fuel container. In particular, it is useful as a multilayer fuel tube or multilayer fuel container for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices. For example, fuel tubes (hoses) such as automobile filler hoses, evaporation hoses, and breather hoses; fuel containers for automobiles, fuel containers for motorcycles, fuel containers for small generators, fuel containers for lawn mowers, etc. Container. A fuel tube (hose) formed from the laminate of the present invention is also one aspect of the present invention.

In addition, the laminated body is further used as an engine body of an automobile engine, a main motion system, a valve system, a lubricant / cooling system, a fuel system, an intake / exhaust system; a drive system transmission system; a chassis steering system; Brake system: Gaskets and non-contact types that require heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance, such as basic electrical parts of control equipment, control system electrical parts, equipment electrical parts, etc. Sealing materials such as contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.) are included.

The sealing material used for the engine body of the automobile engine is not particularly limited, but includes, for example, a cylinder head gasket, a cylinder head cover gasket, an oil pan packing, a gasket such as a general gasket, an O-ring, a packing, a timing belt cover gasket, and the like. For example, a sealing material.

The seal material used in the main motion system of the automobile engine is not particularly limited, and examples thereof include a shaft seal such as a crankshaft seal and a camshaft seal.

The seal material used in the valve system of an automobile engine is not particularly limited, and examples thereof include a valve stem oil seal for an engine valve.

The seal material used in the lubricant / cooling system of the automobile engine is not particularly limited, and examples thereof include a seal gasket of an engine oil cooler.

The sealing material used in the engine fuel system for automobiles is not particularly limited. For example, fuel injection such as an oil seal of a fuel pump, a filler seal of a fuel tank, a tank packing, a connector O link of a fuel tube, etc. Examples thereof include an injector cushion ring, an injector seal ring, an injector O-ring, and a carburetor flange gasket.

The seal material used for the intake / exhaust system of the automobile engine is not particularly limited. For example, the intake manifold packing of the manifold, the exhaust manifold packing, the throttle body packing of the throttle, the turbine shaft seal of the turbo charge, etc. Can be given.

The seal material used in the transmission system of the automobile engine is not particularly limited. For example, bearing seals, oil seals, O-rings, packings, etc. related to transmissions, O-rings, packings, etc. of automatic transmissions. can give.

The sealing material used for the brake system of the engine for automobiles is not particularly limited. For example, oil seals, O-rings, packings, master cylinder piston cups (rubber cups), caliper seals, boots, etc. Etc.

The sealing material used for the electrical equipment for the automobile engine is not particularly limited, and examples thereof include an O-ring and a packing of a car air conditioner.

Applications other than those for automobiles are not particularly limited, for example, oil-resistant, chemical-resistant, heat-resistant, steam- or weather-resistant packings, O-rings, other sealing materials and fuel tubes (hose) in transportation such as ships and airplanes. ), Fuel tanks; similar packings, O-rings, sealing materials and fuel tubes (hoses) in chemical plants, fuel tanks; similar packings, O-rings, sealing materials in food plant equipment and food equipment (including household products) Fuel tube (hose), fuel tank; similar packing, O-ring, seal material and fuel tube (hose) in nuclear plant equipment, fuel tank; Similar packing, O-ring, seal material and fuel tube (hose) in general industrial parts ) And fuel tanks.

The molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable as a fuel peripheral part. In addition, the molded article of the present invention is particularly useful as a sealing material, packing, roller, tube or hose.

The fluororesin composition of the present invention is excellent in adhesiveness with an elastomer, and at the same time has a relatively large MFR and excellent moldability, and does not cause foaming even during high-temperature processing. Since the laminate of the present invention has a fluororesin layer formed from the fluororesin composition and a specific elastomer layer, it can realize high fuel barrier properties and flexibility, and has extremely high adhesion strength between layers.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Preparation of sheet-shaped test piece (fluororesin layer)>
Various fluororesin compositions are set in a mold, held at 260 to 300 ° C. for 15 to 30 minutes with a heat press machine, and after the fluororesin composition is melted, a 3 MPa load is applied for 1 minute and compression molding is performed. Then, a sheet-like test piece having a predetermined thickness was produced.

<Preparation of sheet specimen (elastomer layer)>
Sheet-shaped test pieces having a predetermined thickness were prepared from various elastomer compositions using an 8-inch open roll.

<Production of laminate>
A sheet-shaped test piece of a fluororesin composition having a thickness of 0.5 mm and a sheet-shaped test piece of an elastomer composition having a thickness of 1.5 to 2.0 mm were prepared by the above method. These sheet-like test pieces were stacked and set in a mold heated to 160 ° C., and a load of 3 MPa was applied for 45 minutes at 160 ° C. with a heat press machine to prepare a fluororesin layer-elastomer layer laminate.

<Adhesion evaluation test>
The obtained laminate was cut into strips each having a width of 1.0 cm and a width of 10 cm to produce a test piece for adhesion test, and an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) was used for this test piece. Then, in accordance with the method described in JIS-K-6256 (crosslinking rubber adhesion test method), a peel test was performed at 25 ° C. at a tensile rate of 50 mm / min, and the following criteria were evaluated.

(Adhesion evaluation)
A: The fluororesin layer / elastomer layer interface did not peel, and the fluororesin layer or the elastomer layer was destroyed.
○: Peeled at the fluororesin layer / elastomer layer interface, but was sufficiently adhered and difficult to peel.
Δ: Peeling relatively easily at the fluororesin layer / elastomer layer interface, but adhesion was observed.
X: The fluororesin layer and the elastomer layer did not show adhesiveness at all.

<Functional group analysis by infrared absorption spectrum>
A sheet-like test piece having a thickness of 0.15 to 0.30 mm was prepared by the above method, and an infrared absorption spectrum was analyzed using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by PerkinElmer). The obtained infrared absorption spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of a predetermined peak was measured. The film thickness was measured using a micrometer. Moreover, the difference spectrum with the base resin which does not have a functional group was also used as needed.

<Measurement of composition of fluororesin copolymer>
The copolymer composition of the fluororesin was determined from ¹⁹ F-NMR, fluorine elemental analysis and IR.

<Measurement of fuel permeability coefficient>
A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. 18 mL of CE10 (toluene / isooctane / ethanol = 45/45/10 vol%), which is a simulated fuel, is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the above sheet A test specimen is prepared by setting a cylindrical test piece in the container opening and sealing it. The test specimen was placed in a thermostatic device (60 ° C.), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following formula.

<Measurement of tensile modulus>
A sheet-shaped test piece having a thickness of 2 mm is prepared by the above method, and a dumbbell-shaped test piece having a width of 3.18 mm and a distance between marked lines of 7.6 mm is punched out using an ASTM V type dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. and a tensile speed of 50 mm / min according to ASTM D638 using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation). It was.

<Measurement of melting point of fluororesin>
Using a Seiko differential scanning calorimeter [DSC], the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

<Measurement of melt flow rate (MFR)>
Using a melt indexer (manufactured by Toyo Seiki Seisakusho), the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a 5 kg load at 297 ° C. was measured.

<Confirmation of foaming>
The polymer was allowed to flow out of the nozzle of the melt indexer in the same manner as in the above MFR measurement except that the measurement temperature was 330 ° C., and the foamed state of the obtained polymer strand was observed using a 10 × loupe.
○: Foaming was observed.
X: No foaming was observed.

<Production example>
In the examples and comparative examples, the following materials were used.

(Fluorine resin layer)
Fluororesin (a-1): FEP having a —COOH group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 6.9 g / 10 min. The number of —COOH groups is 480 (per 1 million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-2): FEP having —OC (═O) OCH ₂ CH ₂ CH ₃ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.8 / 7.6 / 0.6 (molar ratio). 261 ° C. The MFR at 297 ° C. is 8.0 g / 10 min. _{-OC (= O) OCH 2 CH} 2 CH 3 radix 410 pieces (carbon atoms per million). Tensile modulus is 460 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ₂ · day).

Fluororesin (a-3): FEP having —CF═CF ₂ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 14.8 g / 10 min. -CF = CF _{2 The} number of groups is 380 (per 1 million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-4): FEP having —CF ₃ group and —CF ₂ H group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 7.8 g / 10 min. -COOH _{group, -OC (= O) OCH 2} CH 2 CH 3 group, -OC (= O) OCH ( CH 3) 2 group, -COF groups, -CF = CF ₂ group, are both -NH ₂ group Less than 20 (per million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-5): CTFE / TFE copolymer having —COOH groups. The monomer composition is CTFE / TFE / perfluoro (propyl vinyl ether) = 77/21/2 (molar ratio). Mp 245 ° C. The MFR at 297 ° C. is 3.0 g / 10 min. The number of —COOH groups is 150 (per 1 million carbon atoms). The tensile modulus is 410 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-6): CTFE / TFE copolymer having —OC (═O) OCH ₂ CH ₂ CH ₃ groups. The monomer composition is CTFE / TFE / perfluoro (propyl vinyl ether) = 77/21/2 (molar ratio). Mp 245 ° C. The MFR at 297 ° C. is 29.5 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 160 (per 1 million carbon atoms). Tensile modulus is 440 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

(Elastomer layer)
Elastomer composition (b-1): NBR full compound. 100 parts by mass of acrylonitrile-butadiene rubber (N530, manufactured by JSR Corporation), 43 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 7 parts by mass of zinc oxide (manufactured by Hystec Co., Ltd.), wet silica (Nipsil VN3, Nippon Silica Kogyo Co., Ltd.) 21 parts by mass, stearic acid (Lunac, Kao Co., Ltd.) 1.4 parts by mass, anti-aging agent (A.O.224, manufactured by KING INDUSTRIES) 3 parts by mass, plasticizer ( Thiokol TP95, manufactured by Morton International 21 parts by mass, wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.) 3 parts by mass is added to an 8-inch open roll. Was used for kneading to obtain an elastomer composition (b-1).

Elastomer composition (b-2): NBR full compound. 100 parts by mass of acrylonitrile-butadiene rubber (N530, manufactured by JSR Corporation), 43 parts by mass of carbon black (N990, manufactured by Cancarb Ltd.), 7 parts by mass of zinc oxide (manufactured by Hystec Corporation), wet silica (Nipsil VN3, Nippon Silica Kogyo Co., Ltd.) 21 parts by mass, stearic acid (Lunac, Kao Co., Ltd.) 1.4 parts by mass, anti-aging agent (A.O.224, manufactured by KING INDUSTRIES) 3 parts by mass, plasticizer ( Thiokol TP95, 21 parts by mass from Morton International, wax (carnauba wax, manufactured by Toa Kasei Co., Ltd.), peroxide (Park Mill D-40, manufactured by Nippon Oil & Fats Co., Ltd.), 3 parts by mass, V3 (Daikin Industries, Ltd.) 6 parts by mass, Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.) Added and kneaded using an 8-inch open roll to obtain an elastomer composition (b-2).

Elastomer composition (b-3): FKM full compound. Ternary fluororubber raw rubber (G-558BP, manufactured by Daikin Industries, Ltd., VdF / TFE / HFP = 58/20/22 mol%) to 100 parts by mass of bisphenol AF (manufactured by Daikin Industries) 2.2 parts by mass , DBU-B (manufactured by Wako Pure Chemical Industries, Ltd.) 0.56 parts by mass, carbon black (seest S, manufactured by Tokai Carbon Co., Ltd.), 13 parts by mass, magnesium oxide (Kyowa Mag 150, manufactured by Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass and 6.0 parts by mass of calcium hydroxide (Caldic 2000, manufactured by Omi Chemical Co., Ltd.) were added and kneaded using an 8-inch open roll to obtain an elastomer composition (b-3). It was.

Elastomer composition (b-4): ECO full compound. Epichlorohydrin rubber (Epichromer CG, manufactured by Daiso Corporation) 100.0 parts by mass, carbon black (N-550, manufactured by Cancarb Ltd.) 80 parts by mass, Plasticizer (ADK Cizer RS-107, Asahi Denka Kogyo Co., Ltd.) 5.0 parts by mass, Lubricant (Splender R-300) 2.0 parts by mass, anti-aging agent (NOCRACK NBC, Ouchi Shinsei Chemical Co., Ltd.) 2.0 parts by mass, synthetic hydrotalcite (DHT-4A, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, magnesium oxide (Kyowa Mag 150, Kyowa Chemical Industry Co., Ltd.) 3.0 parts by mass, DBU phenol resin salt (P-152) 1.5 parts by mass, 6-methyl Quinoxaline-2,3-dithiocarbonate (Daisonette XL-21S, manufactured by Daiso Corporation) 1.5 parts by mass was added and kneaded using an 8-inch open roll to obtain an elastomer composition (b-4).

Example 1
After 80 g of fluororesin (a-1) was melted in a lab plast mill (produced by Toyo Seiki Seisakusho Co., Ltd.) having an internal volume of 80 ml heated to 280 ° C., 3,4′-DPE (Wakayama Seika Co., Ltd.) )) 0.64 g was added and melt-kneaded for 10 minutes to obtain a fluororesin composition. From the infrared absorption spectrum, since an absorption band of 1744 cm ⁻¹ that was not observed in the fluororesin (a-1) was observed, at least a part of the fluororesin (a-1) and 3,4′-DPE was observed. It was suggested that is bound by an amide bond.

The tensile elasticity modulus, fuel permeability coefficient, and MFR of the obtained fluororesin composition were measured to evaluate the presence or absence of foaming. The results are shown in Table 1.

Using the fluororesin composition and the elastomer composition (b-1 to 4), a laminate was produced according to the above method. The adhesion of this laminate was evaluated by the above method. The results are shown in Table 1.

Examples 2-9, Comparative Examples 1-3
A fluororesin composition was obtained in the same manner as in Example 1 except that the fluororesin and polyfunctional compound shown in Table 1 were used. MFR of the obtained fluororesin composition was measured and the presence or absence of foaming was evaluated. Moreover, the laminated body was created like Example 1 and adhesiveness was evaluated. The results are shown in Table 1.

Example 10 (dynamic crosslinking)
Fluorine rubber (ternary rubber comprising 50% by mole of vinylidene fluoride, 20% by mole of tetrafluoroethylene and 30% by mole of hexafluoropropylene; Mooney viscosity at 100 ° C. = 88) 2.0 parts by mass of bis (4-hydroxyphenyl) perfluoropropane (“Bisphenol AF” manufactured by Daikin Industries, Ltd.), benzyltriphenylphosphonium chloride (BTPPC, manufactured by Hokuko Chemical Co., Ltd.) as a crosslinking accelerator 0 part by mass and 3 parts by mass of magnesium oxide (Kyowa Mag 150 Kyowa Chemical Industry Co., Ltd.) were added and kneaded using an 8-inch open roll to obtain a fluororubber composition.

Next, after premixing 1.1 parts by mass of TFDPE (manufactured by Wakayama Seika Co., Ltd.) with 100 parts by mass of the fluororesin (a-6) by a dry blend method, 80 parts by mass of the fluororesin composition And 20 parts by mass of the fluororubber composition are fed from a separate feeder to a twin-screw extruder (φ = 15 mm, L / D = 60) and melted under conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 700 rpm. Kneaded. The strand coming out of the die was water-cooled in a cooling water tank, and cut with a pelletizer to obtain a fluororesin composition containing a dynamically crosslinked fluororubber in the form of a pellet.

MFR of the obtained fluororesin composition was measured and the presence or absence of foaming was evaluated. Moreover, the laminated body was created like Example 1 and adhesiveness was evaluated. The results are shown in Table 1.

The fluororesin composition of the present invention can be suitably used for forming a fluororesin layer in a laminate having a fluororesin layer and an elastomer layer. The laminate of the present invention can be suitably used as a molded body such as a fuel tube.

Claims (10)

A fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer, and an aromatic asymmetric polyfunctional compound,
The aromatic resin asymmetric polyfunctional compound is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the fluororesin. The fluororesin composition according to claim 1, wherein the aromatic asymmetric polyfunctional compound has a fluorine atom. Furthermore, the fluororesin composition of Claim 1 or 2 containing a fluororubber. The fluororesin is at least one selected from the group consisting of a copolymer composed of tetrafluoroethylene and hexafluoropropylene, a copolymer composed of ethylene and tetrafluoroethylene, and a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene. The fluororesin composition according to claim 1, 2 or 3, which is a seed. A fluororesin layer (a) formed from the fluororesin composition according to claim 1, 2, 3 or 4,
An elastomer layer (b) formed from an elastomer composition;
The laminated body characterized by including. The elastomer compositions include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber and acrylic. The laminate according to claim 5, comprising at least one elastomer selected from the group consisting of rubber. The laminate according to claim 4 or 5, wherein the elastomer composition contains at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin. A molded article formed from the laminate according to claim 5, 6 or 7. A fuel tube formed from the laminate according to claim 5, 6 or 7. The manufacturing method of the laminated body of Claim 5, 6 or 7.